KR102460745B1 - Laminate, container and manufacturing method thereof, and sheet for use as raw material of laminate - Google Patents

Abstract

Provided is a laminate having excellent transparency and capable of manufacturing a container with high cold-resistant impact strength and rigidity. A propylene-based polymer (A): 60.0 mass% or more and 85.0 mass% or less, and an ethylene-based polymer (B): a resin layer [I] comprising a resin composition [I] comprising 15.0 mass% or more and 40.0 mass% or less, and a propylene-based polymer Polymer (A): 80.0 mass % or more and 99.9 mass % or less, ethylene polymer (B): 0.0 mass % or more and less than 15.0 mass %, and nucleating agent (C): 0.1 mass % or more and 20.0 mass % or less Resin composition [II ], wherein in both of the resin compositions [I] and [II], the propylene-based polymer (A) and the ethylene-based polymer (B) are A laminate that satisfies the requirements.

Description

A laminated body, a container, its manufacturing method, and the sheet|seat for laminated body raw materials TECHNICAL FIELD

The present invention relates to a laminate, a container, a method for manufacturing the same, and a sheet for a raw material for a laminate.

As a packaging container for foods such as jelly, pudding, and coffee (hereinafter also referred to as a food packaging container), there is a demand for a container with good visibility of contents, ie, excellent transparency. As a raw material of the container excellent in transparency, the propylene-type resin composition excellent in heat resistance, rigidity, and transparency is used.

On the other hand, since food is often handled in a low-temperature environment in its storage and distribution, food packaging containers are required not only to have impact resistance at room temperature, but also impact resistance at low temperatures, that is, low-temperature impact resistance.

As a propylene resin composition excellent in impact resistance, the composition containing, for example, a propylene-ethylene block copolymer, a nucleating agent, and a low density polyethylene resin or a linear low density polyethylene resin is known (refer patent document 1).

As a propylene-type resin composition excellent in low-temperature impact resistance, the composition which consists of a propylene block copolymer and an ethylene-type resin, for example and has specific physical properties is known (refer patent documents 2, 3).

Japanese Patent Laid-Open No. 2001-26686 Japanese Patent Laid-Open No. 2002-187996 Japanese Patent Laid-Open No. 2002-187997

A container obtained by vacuum molding or air pressure molding of a propylene-based resin composition is excellent in transparency and is used for beverage applications and the like. However, since polypropylene alone has low cold-resistant impact strength, the container may break during transportation at low temperatures. On the other hand, when an ethylene-based polymer is blended, the cold-resistant impact strength is improved, but the transparency is lowered, and in particular, when the blending ratio of the ethylene-based polymer is high, the rigidity is lowered.

An object of the present invention is to provide a laminate that is excellent in transparency, and can produce a container with high cold-resistant impact strength and rigidity.

The present invention is the following [1] to [11].

[1] Propylene-based polymer (A): 60.0 mass% or more and 85.0 mass% or less and ethylene-based polymer (B): 15.0 mass% or more and 40.0 mass% or less (provided that (A) + (B) = 100.0 mass%) A resin layer [I] comprising a resin composition [I] comprising:

Propylene-based polymer (A): 80.0 mass% or more and 99.9 mass% or less, and ethylene-based polymer (B): 0.0 mass% or more and less than 15.0 mass% and nucleating agent (C): 0.1 mass% or more and 20.0 mass% or less (provided that ( A) + (B) + (C) = 100.0 mass%) resin layer [II] containing the resin composition [II]

As a laminate comprising a,

In both of the resin compositions [I] and [II], the propylene-based polymer (A) and the ethylene-based polymer (B) satisfy the following requirements (i) to (iv).

Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.

Requirement (ii): The content of α-olefins other than propylene in the propylene-based polymer (A) determined by infrared spectroscopy is 0 to 5% by mass.

Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .

Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0.

[2] In both of the resin compositions [I] and [II], the ethylene-based polymer (B) has a density of 891 to 945 kg/m ³ ethylene-based polymer (B1): 50.0 to 100.0 mass% and a density of 890 kg /m ³ or less ethylene polymer (B2): The laminate according to [1], which is a composition comprising 0.0 to 50.0 mass % (provided that (B1) + (B2) = 100.0 mass %).

[3] The laminate consists of the resin layer [I] and the resin layer [II],

The laminate according to [1] or [2], wherein the ratio of the thickness of the resin layer [I] to the resin layer [II] (resin layer [II]/resin layer [I]) is 1/198 to 1/3. .

[4] The resin layer [II], the resin layer [I], and the resin layer [II] are laminated in this order,

The laminate according to [1] or [2], wherein the ratio of the thickness of each layer (resin layer [II]/resin layer [I]/resin layer [II]) is 1/198/1 to 1/3/1.

[5] The laminate according to any one of [1] to [4], wherein the laminate has a thickness of 3 mm or less.

[6] The laminate according to any one of [1] to [5], wherein the α-olefin content other than propylene in the requirement (ii) is an ethylene content.

[7] A container comprising the laminate according to any one of [1] to [6].

[8] The container according to [7], wherein the resin layer [II] has a thickness of 1.5 µm or more.

[9] The container according to [7] or [8], obtained by vacuum pressure molding the laminate.

[10] A method for manufacturing a container in which the laminate according to any one of [1] to [6] is subjected to vacuum forming, air pressure forming, or vacuum air pressure forming to obtain a container.

[11] Propylene-based polymer (A): 60.0 mass% or more and 85.0 mass% or less, and ethylene-based polymer (B): 15.0 mass% or more and 40.0 mass% or less (provided that (A) + (B) = 100.0 mass%) A sheet for a laminate raw material that satisfies the following requirements (i) to (v).

Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.

Requirement (ii): The content of α-olefins other than propylene in the propylene-based polymer (A) determined by infrared spectroscopy is 0 to 5% by mass.

Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .

Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0.

Requirement (v): The thickness of the said sheet|seat for laminated body raw materials is 2.97 mm or less.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in transparency, and the laminated body which can manufacture a container with high cold-resistant impact strength and rigidity can be provided.

[Laminate]

The laminate according to the present invention includes a resin layer [I] and a resin layer [II]. This resin layer [I] contains the resin composition [I] which consists of a propylene-type polymer (A): 60.0 mass % or more and 85.0 mass % or less, and an ethylene-type polymer (B): 15.0 mass % or more and 40.0 mass % or less. On the other hand, in the resin composition [I], the total of the propylene-based polymer (A) and the ethylene-based polymer (B) is 100.0% by mass. In addition, this resin layer [II] contains a propylene-based polymer (A): 80.0 mass% or more and 99.9 mass% or less, an ethylene-based polymer (B): 0.0 mass% or more and less than 15.0 mass%, and a nucleating agent (C): 0.1 mass% The resin composition [II] which consists of more than 20.0 mass % is included. On the other hand, in resin composition [II], the sum total of a propylene-type polymer (A), an ethylene-type polymer (B), and a nucleating agent (C) is 100.0 mass %.

Here, the propylene polymer (A) contained in the resin composition [I] and the propylene polymer (A) contained in the resin composition [II] may be the same or different. The ethylene polymer (B) contained in the resin composition [I] and the ethylene polymer (B) contained in the resin composition [II] may be the same or different. Moreover, the laminated body should just contain the resin layer [I] and the resin layer [II] at least. For example, the laminate may have a two-layer structure in which one resin layer [I] and one resin layer [II] are laminated, and one resin layer [II] and one resin layer [I] and a three-layer structure in which the resin layer [II] of one layer is laminated in this order may be sufficient.

In the present invention, in both the resin composition [I] and the resin composition [II], the propylene-based polymer (A) and the ethylene-based polymer (B) satisfy the following requirements (i) to (iv) make it

Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.

Requirement (ii): The content of α-olefins other than propylene in the propylene-based polymer (A) determined by infrared spectroscopy is 0 to 5% by mass.

Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .

Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0.

When the ethylene-based polymer (B) is blended with the propylene-based polymer (A) from the viewpoint of improving cold-resistant impact strength, even if it is transparent in the laminated state, it is formed into a container shape by molding such as vacuum molding, The particle|grains of the said ethylene polymer (B) disperse|distributed in the said propylene-type polymer (A) generate|occur|produce unevenness on the surface of a container, and transparency falls. Such an incompatible resin composition WHEREIN: It is thought that the cause of a transparency fall is the internal haze resulting from the resin interface normally. However, the present inventors discovered that the main cause of transparency fall existed in the surface unevenness|corrugation (external haze). Then, in order to suppress the unevenness|corrugation (external haze) of the said surface, the present inventors provide the said resin layer [II] with little content of the said ethylene polymer (B) on the outside of the said resin layer [I], Surface irregularities were suppressed.

That is, in the present invention, the resin compositions [I] and [II] containing the propylene-based polymer (A) and the ethylene-based polymer (B) in a predetermined composition satisfying the requirements (i) to (iv) are prepared. , It is possible to provide a laminate which is excellent in transparency and can manufacture a container with high cold-resistant impact strength and rigidity by using each as a raw material of the resin layers [I] and [II]. On the other hand, when the resin composition [II] does not contain the ethylene-based polymer (B), the resin composition [II] may satisfy the above requirements (i) and (ii).

(Propylene-based polymer (A))

The propylene-based polymer (A) according to the present invention is not particularly limited as long as it contains 50% by mass or more of propylene units and satisfies the above requirements (i), (ii) and (iv). Examples of the propylene-based polymer (A) include homopolypropylene (homo PP), which is a propylene homopolymer, propylene/α-olefin random copolymer (random PP), and the like. In addition, the propylene-type polymer (A) may be a composition containing two or more types of propylene-type polymers.

Examples of the α-olefin in the propylene/α-olefin random copolymer include ethylene and α-olefin having 4 to 20 carbon atoms. Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, and 1-tetradecene. , 1-hexadecene, 1-octadecene, 1-eicosene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene , diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, di Ethyl-1-hexene, trimethyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl -1-heptene, ethyl-1-octene, methyl-1-nonene, and the like. These may use 1 type and may use 2 or more types together. Among these, ethylene and C4-C8 alpha-olefin are preferable, and ethylene is more preferable.

Specific examples of the propylene/α-olefin random copolymer include a propylene/ethylene random copolymer, a propylene-1-butene random copolymer, a propylene-1-pentene random copolymer, a propylene-1-hexene random copolymer, and a propylene/ethylene random copolymer. 1-octene random copolymer, propylene/ethylene/1-butene random copolymer, etc. are mentioned. These may use 1 type and may use 2 or more types together. Among these, a propylene/ethylene random copolymer is preferable. The content of the α-olefin unit in the propylene/α-olefin random copolymer is preferably 5% by mass or less.

As Homo PP and Random PP, commercially available products include PM series, PL series, PC series (trade name, manufactured by Sunalloy Co., Ltd.), Prime Polypro (trade name, made by Prime Polymer), Novatec (brand name, manufactured by Nippon Polypro Co., Ltd.) )), E-200GP (trade name, manufactured by Prime Polymer Corporation), E-330GV (trade name, manufactured by Prime Polymer Corporation), F107DJ (trade name, manufactured by Prime Polymer Corporation), B241 (trade name, manufactured by Prime Polymer Corporation), and the like. These may use 1 type and may use 2 or more types together.

<Requirement (i)>

The melt flow rate (MFR) of the propylene-based polymer (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 is 0.1 to 12.0 g/10 min, preferably 0.6 to 7.0 g/10 min, and 1.0 -5.0 g/10 min is more preferable, and 1.5-3.0 g/10 min is still more preferable. When the MFR is outside the range of 0.1 to 12.0 g/10 min, the moldability deteriorates and molding cannot be performed. Moreover, the cold-resistant impact strength of the container obtained from the laminated body which concerns on this invention falls.

<Requirement (ii)>

Content of alpha-olefins other than propylene calculated|required by infrared spectroscopy of a propylene-type polymer (A) is 0-5 mass %, 0-4 mass % is preferable, and its 0-3 mass % is more preferable. When the content of α-olefins other than propylene exceeds 5% by mass, rigidity decreases. The ?-olefin other than propylene is preferably an ?-olefin having 2 and 4 to 10 carbon atoms, more preferably an ?-olefin having 2 or 4 carbon atoms, and still more preferably ethylene. As the propylene polymer (A) having an α-olefin content other than propylene within the above range, for example, homo PP, random PP having an α-olefin content other than propylene of 5% by mass or less, homo PP and α-olefin content other than propylene The composition etc. containing this 5 mass % or less random PP are mentioned. In addition, 0 mass % may be sufficient as content of alpha-olefin other than this propylene. That is, the propylene-based polymer (A) does not need to contain an ?-olefin unit other than propylene. In addition, the α-olefin content other than the propylene is a value calculated by the method described later. On the other hand, when ethylene content is calculated|required as an example of alpha-olefin other than propylene, the wavelength in infrared spectroscopy is 718 cm ^-1 and 733 cm ^-1 . In addition, the wavelength used for the measurement of alpha-olefins other than ethylene is generally known.

(Ethylene-based polymer (B))

The ethylene-based polymer (B) according to the present invention is not particularly limited as long as it contains 50% by mass or more of ethylene units and satisfies the above requirements (iii) and (iv). Examples of the ethylene-based polymer (B) include an ethylene homopolymer, an ethylene/α-olefin copolymer, and the like. In addition, the composition containing two or more types of ethylene polymers may be sufficient as an ethylene polymer (B).

Examples of the α-olefin in the ethylene/α-olefin copolymer include α-olefins having 3 to 20 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -Octadecene, 1-eicosene, 4-methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene , trimethyl-1-butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, tri Methyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl- 1-octene, methyl-1-nonene, etc. are mentioned. Among these, ?-olefins having 3 to 8 carbon atoms are preferable, and propylene, 1-butene, and 1-octene are more preferable. The ethylene polymer (B) may contain 1 type of these units, and may contain 2 or more types.

Specific examples of the ethylene/α-olefin copolymer include an ethylene/propylene random copolymer and an ethylene/1-butene random copolymer. Among these, an ethylene/propylene random copolymer is preferable.

As the ethylene-based polymer (B), commercially available products include Evolu (trade name, manufactured by Prime Polymer Co., Ltd.), Harmorex (trade name, manufactured by Nippon Polyethylene Co., Ltd.), Kernel (trade name, manufactured by Nippon Polyethylene Co., Ltd.), Novatec (trade name, manufactured by Nippon Polyethylene Co., Ltd.), Elite, Dowlex, Affinity, Attane (trade name, manufactured by Dow Chemical), Exceed, Enable (trade name, manufactured by Exxon Chemical), SP1520 (brand name, manufactured by Prime Polymer), SP0510 ( and SP1071C (trade name, manufactured by Prime Polymer), SP2510 (trade name, manufactured by Prime Polymer), and A1085 (trade name, manufactured by Mitsui Chemicals). These may use 1 type and may use 2 or more types together.

<Requirement (iii)>

The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ , preferably 895 to 918 kg/m ³ , and more preferably 900 to 910 kg/m ³ . When the said density is less than 890 kg/m< ³ >, rigidity falls. Moreover, when the said density exceeds 920 kg/m< ³ >, transparency falls and cold-resistant impact strength also falls.

Further, in both of the resin compositions [I] and [II], the ethylene-based polymer (B) has a density of 891 to 945 kg/m ³ of the ethylene-based polymer (B1): 50.0 to 100.0 mass% and a density of 890 kg/m ³ It is preferable from a viewpoint of rigidity that it is a composition which consists of the following ethylene polymers (B2):0.0-50.0 mass %. Here, ethylene-type polymer (B1) + ethylene-type polymer (B2) = 100.0 mass %. 895-925 kg/m< ³ > is preferable and, as for the density of an ethylene polymer (B1), 900-920 kg/m< ³ > is more preferable. 855-888 kg/m< ³ > is preferable and, as for the density of an ethylene-type polymer (B2), 870-886 kg/m< ³ > is more preferable.

The blending ratio of the ethylene-based polymer (B1) and the ethylene-based polymer (B2) is preferably 55.0 to 95.0% by mass of the ethylene-based polymer (B1), 5.0 to 45.0% by mass of the ethylene-based polymer (B2), and the ethylene-based polymer ( B1): 60.0 to 90.0 mass %, ethylene polymer (B2): 10.0 to 40.0 mass % is more preferable, ethylene polymer (B1): 65.0 to 85.0 mass %, ethylene polymer (B2): 15.0 to 35.0 mass % % is more preferable. When the above compounding ratio is satisfied, transparency and rigidity of the laminate and container are high.

<Requirement (iv)>

MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the ethylene-based polymer (B) The ratio of one MFR(B) (MFR(A)/MFR(B)) is 0.2 to 5.0, preferably 0.3 to 4.0, more preferably 0.4 to 3.0, and still more preferably 0.6 to 1.5. When MFR(A)/MFR(B) is outside the range of 0.2-5.0, transparency of a laminated body and a container will fall. Moreover, when MFR(A)/MFR(B) is less than 0.2, the cold-resistant impact strength of a container falls.

(nucleating agent (C))

In the present invention, the resin composition [II] forming the resin layer [II] contains a nucleating agent (C). In addition, the resin layer [I] may also contain a nucleating agent.

Although there is no limitation in particular as a nucleating agent (C), A sorbitol-type nucleating agent, a phosphorus-type nucleating agent, a carboxylate-type nucleating agent, a polymer nucleating agent, an inorganic compound, etc. can be used. As the nucleating agent (C), it is preferable to use a sorbitol-based nucleating agent, a phosphorus-based nucleating agent, or a polymer nucleating agent.

Examples of the sorbitol-based nucleating agent include nonitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] (nonitol 1,2, 3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]), 1,3,2,4-dibenzylidenesorbitol, 1,3,2,4-di- (p-methylbenzylidene)sorbitol and 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol can be used.

Examples of the phosphorus-based nucleating agent include sodium-bis-(4-t-butylphenyl)phosphate, potassium-bis-(4-t-butylphenyl)phosphate, sodium-2,2'-ethylidene-bis(4). ,6-di-t-butylphenyl)phosphate, sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl)phosphate, bis(2,4,8,10-tetra-t- Butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphosine-6-oxide) aluminum hydroxide salt can be used.

As a carboxylate metal salt type nucleating agent, p-t- butyl benzoate aluminum, aluminum adipate, and sodium benzoate can be used, for example.

As the polymer nucleating agent, a branched α-olefin polymer is preferably used. Examples of the branched α-olefin polymer include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, and 4-methyl-1- A homopolymer of hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, or 3-ethyl-1-hexene, or a copolymer thereof, further and copolymers of these and other ?-olefins. The polymer of 3-methyl-1-butene is preferable from a viewpoint of transparency, cold-resistant impact strength, rigidity, and economical efficiency.

As an inorganic compound, talc, mica, and calcium carbonate can be used, for example.

Among these nucleating agents, from the viewpoint of high transparency, cold-resistant impact strength and rigidity, and low odor, nonitol, 1,2,3-trideoxy-4,6:5,7-bis as the nucleating agent (C) -O-[(4-propylphenyl)methylene], bis(2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2] It is preferable to use dioxaphosphosine-6-oxide) aluminum hydroxide salt. These nucleating agents may be used individually by 1 type, and may use 2 or more types together.

As the nucleating agent (C), a commercial item can be used. For example, nonitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene] is a trade name of Milard NX8000 (manufactured by Milliken Corporation). is being marketed. Adecastab NA-21 (trade name, manufactured by Adeka Corporation) is bis(2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo[d,g][1,3,2] ] Contains dioxaphosphosine-6-oxide) aluminum hydroxide salt as a main component.

In the laminate according to the present invention, when the resin layer [II] contains the nucleating agent (C) in a predetermined amount, the rigidity and transparency of the container formed using the laminate are improved. By containing a predetermined amount of a nucleating agent (C), since the spheroid size of the crystal|crystallization in resin composition [II] becomes small and diffuse reflection of light is reduced, it is estimated that transparency improves. Moreover, it is estimated that rigidity becomes high by the improvement of crystallinity.

(resin layer [I])

The resin layer [I] according to the present invention includes a resin composition [I]. The resin layer [I] may consist of a resin composition [I]. The said resin composition [I] consists of propylene-type polymer (A): 60.0 mass % or more and 85.0 mass % or less, and ethylene-type polymer (B): 15.0 mass % or more and 40.0 mass % or less. Here, propylene-type polymer (A) + ethylene-type polymer (B) = 100.0 mass %. The resin composition [I] preferably consists of propylene-based polymer (A): 65.0 mass% or more and 83.0 mass% or less and ethylene-based polymer (B): 17.0 mass% or more and 35.0 mass% or less, propylene-based polymer (A): It is more preferable to consist of 70.0 mass % or more and 80.0 mass % or less, and ethylene-type polymer (B): 20.0 mass % or more and 30.0 mass % or less.

When content of an ethylene-type polymer (B) is less than 15.0 mass %, it is inferior to cold-resistant impact strength. When content of an ethylene-type polymer (B) exceeds 40.0 mass %, transparency and rigidity will fall.

(resin layer [II])

The resin layer [II] according to the present invention includes a resin composition [II]. The resin layer [II] may consist of a resin composition [II]. The said resin composition [II] contains a propylene polymer (A): 80.0 mass % or more and 99.9 mass % or less, an ethylene polymer (B): 0.0 mass % or more and less than 15.0 mass %, and a nucleating agent (C): 0.1 mass % or more 20.0 % or less by mass. Here, propylene-type polymer (A) + ethylene-type polymer (B) + nucleating agent (C) = 100.0 mass %. In addition, the resin composition [II] does not need to contain an ethylene-type polymer (B). Resin composition [II] contains: propylene-based polymer (A): 85.0 mass% or more and 99.9 mass% or less, ethylene-based polymer (B): 0.0 mass% or more and 13.0 mass% or less, and nucleating agent (C): 0.1 mass% or more and 15.0 mass% % or less, propylene-based polymer (A): 89.9 mass% or more and 99.9 mass% or less, ethylene-based polymer (B): 0.0 mass% or more and 10.0 mass% or less, and nucleating agent (C): 0.1 mass% or more It is more preferable to consist of 10.0 mass % or less.

When content of an ethylene polymer (B) is 15.0 mass % or more, transparency and rigidity fall. When content of a nucleating agent (C) is less than 0.1 mass %, rigidity and transparency fall. Even if the content of the nucleating agent (C) exceeds 20.0% by mass, the effect of further improving the physical properties is small and not economical.

(laminate)

The laminate according to the present invention includes a resin layer [I] and a resin layer [II]. The laminate may contain at least the resin layer [I] and the resin layer [II], and may contain layers other than the resin layer [I] and the resin layer [II]. However, it is preferable that a laminated body has a two-layer structure in which the resin layer [I] of one layer and the resin layer [II] of one layer were laminated|stacked from a cold-resistant impact strength and a transparency viewpoint. Further, the laminate has a three-layer structure in which one resin layer [II], one resin layer [I], and one resin layer [II] are laminated in this order from the viewpoint of cold resistance impact strength and transparency. It is preferable to have Moreover, it is preferable from a transparency viewpoint that the resin layer [II] forms the surface of a laminated body.

When the laminate consists of a resin layer [I] and a resin layer [II] (two-layer structure), the ratio of the thickness of the resin layer [I] and the resin layer [II] (resin layer [II]/resin layer [I]) It is preferable that it is 1/198 - 1/3, and it is more preferable that it is 1/12 - 1/5. When this ratio is 1/198 or more, transparency of a laminated body and a container improves. Moreover, when the said ratio is 1/3 or less, the cold-resistant impact strength of a laminated body and a container improves.

When the laminate is laminated with a resin layer [II], a resin layer [I], and a resin layer [II] in this order (three-layer structure), the ratio of the thickness of each layer (resin layer [II]/resin layer [ I]/resin layer [II]) is preferably 1/198/1 to 1/3/1, more preferably 1/12/1 to 1/5/1. When this ratio exists in the said range, transparency of a laminated body and a container, and cold-resistant impact strength improve. In addition, this ratio shows the ratio in case the thickness of two resin layers [II] is the same.

It is preferable that they are 3 mm or less, and, as for the thickness of a laminated body, it is more preferable that they are 0.1 mm or more and 2 mm or less. When the thickness of the laminate is 3 mm or less, the laminate can be easily molded into a container by the vacuum pressure forming method described later.

(Method for producing a laminate)

When manufacturing the laminate according to the present invention, for example, after measuring a predetermined amount of the propylene-based polymer (A) and the ethylene-based polymer (B) so as to have a blending ratio within the above range, it may be directly put into the hopper of a sheet forming machine. . In addition, the raw material after the above measurement is mixed in advance using a ribbon blender, Banbury mixer, Henschel mixer, super mixer, etc., and further melt-kneaded using a compounding machine or kneader such as a single screw or twin screw extruder or a roll, You may shape|mold into a sheet form.

In the present invention, a film or sheet form by a method used in the production of a propylene-based resin film or sheet, for example, an extrusion method such as a T-die method or an inflation method, a calender method, a casting method, or the like. can be molded into

[Container and its manufacturing method]

The container according to the invention consists of the laminate according to the invention. The container which concerns on this invention can be used suitably as a food packaging container, such as a beverage handled in a low-temperature environment, for example. The container according to the present invention can be obtained by molding the laminate according to the present invention by any molding method such as vacuum forming, air pressure forming, or vacuum air forming. However, it is preferable from a viewpoint of transparency to carry out vacuum pressure molding of a laminated body to obtain a container. Moreover, it is preferable from a viewpoint of transparency that resin layer [II] forms the surface of a container. It is preferable that it is 1.5 micrometers or more, and, as for the thickness of the resin layer [II] which forms a container, it is more preferable that they are 10 micrometers or more and 100 micrometers or less. When the thickness of the resin layer [II] is 1.5 µm or more, the cold-resistant impact strength of the container is improved.

[Sheet for laminate material]

The sheet for a raw material for a laminate according to the present invention contains a propylene-based polymer (A): 60.0% by mass or more and 85.0% by mass or less and an ethylene-based polymer (B): 15.0% by mass or more and 40.0% by mass or less (provided that (A)+(B) ) = 100.0 mass %). Moreover, this sheet|seat for laminated body raw materials satisfy|fills the following requirements (i)-(v). The sheet for a raw material for a laminate according to the present invention can be suitably used as the resin layer [I] in the laminate according to the present invention.

Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.

Requirement (ii): The content of α-olefins other than propylene in the propylene-based polymer (A) determined by infrared spectroscopy is 0 to 5% by mass.

Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .

Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0.

Requirement (v): The thickness of the said sheet|seat for laminated body raw materials is 2.97 mm or less.

The requirements (i) to (iv) are the same as the requirements (i) to (iv) described above.

The said requirement (v) WHEREIN: The thickness of the said sheet|seat for laminated body raw materials is 2.97 mm or less, 2.50 mm or less is preferable, and 2.30 mm or less is more preferable. When the thickness of the said sheet|seat for laminated body raw materials is 2.97 mm or less, transparency at the time of setting it as a container is favorable. In addition, although the minimum of the thickness of the said sheet|seat for laminated body raw materials is not specifically limited, For example, it can be 0.80 mm or more.

Moreover, the said sheet|seat for laminated body raw materials may contain the nucleating agent (C) as an arbitrary component.

Example

The physical properties of the polymer used in the Examples and Comparative Examples of the present invention and the physical properties of the container were measured by the following method.

<Melt flow rate (MFR)>

The melt flow rate (MFR) of the propylene-based polymer and the ethylene-based polymer was measured in accordance with JIS K6921 under conditions of a temperature of 230°C and a load of 21.18N.

<Density>

In accordance with JIS K6922, the density of the ethylene-based polymer was measured by heating the measurement sample at 100°C for 30 minutes, then holding it at 23°C for 1 hour and using the density gradient tube method.

<Ethylene content in propylene polymer>

The ethylene content in the propylene polymer is determined by the following formula from the absorbance at 718 cm ^-1 and 733 cm ^-1 by preparing a sheet of propylene polymer having a thickness of 300 μm under the following conditions, and using FT/IR5300 (trade name, manufactured by Nippon Spectroscopy). was calculated by

・Sheet forming conditions

Press temperature: 220℃

Pressing pressure during hot/cold pressure: 50kg/cm ² G

Preheat: 5min; Pressurization: 5min; Cold pressure: 3min

・IR measurement conditions

Integration count: 20 times; Resolution: 4cm ^-1

・Ethylene content (χ (mass %))

χ=0.809×(χ1+χ2)

χ1 = 0.599×(A733/d·l)-0.161×(A718/d·l)

χ2 = 0.599×(A718/d·l)-0.161×(A733/d·l)

A718: Absorbance of 718cm ^-1

A733: Absorbance of 733 cm ^-1

d: 0.9, l: thickness of the sample.

<Physical properties of the container>

(1) Transparency

About the body part (average thickness of 300-400 micrometers) of a cup-shaped container, based on JISK7136, the haze was measured. On the other hand, the total haze is the sum of the internal haze and the external haze.

(2) Cold-resistant impact strength

150 g of ethylene glycol was put in a cup-shaped container, the upper part was heat-sealed with a PP sheet, and it preserve|saved for one day in a low-temperature thermostat (-30 degreeC). Then, the cup-shaped container was taken out from the said low-temperature thermostat, and the maximum fall height at which the cup-shaped container does not break was evaluated.

(3) rigidity

The tensile modulus of elasticity of the body portion (average thickness of 300 to 400 µm) of the cup-shaped container was measured in accordance with JIS K7113-2. In addition, the said measurement was performed about the extrusion direction (MD) of vacuum press molding, and the perpendicular|vertical direction (TD) of MD.

[Example 1]

(A-1): 50.0 mass% and (A-2): 25.0 mass% shown in Table 1 as the propylene-based polymer (A), and (B-2) shown in Table 1 as the ethylene-based polymer (B) : 20.0 mass % and (B-5): 5.0 mass % were dry-blended, and resin composition [I] was obtained. Further, as the propylene-based polymer (A), (A-2) shown in Table 1: 99.0% by mass, and as the nucleating agent (C), Millard R8000 (trade name, Dainichi Seika Co., Ltd., sorbitol-based nucleating agent): 1.0 The mass % was dry-blended to obtain a resin composition [II]. Using the resin composition [I] as a raw material for the resin layer [I], and the resin composition [II] as a raw material for the resin layer [II], using a multilayer sheet molding machine (manufactured by Shinko Corporation), the resin layer [ II] (surface layer), a resin layer [I] (intermediate layer), and a resin layer [II] (surface layer) were laminated in this order to obtain a sheet-like laminate. Specifically, the raw material is melt-extruded at a temperature of 250°C so that the ratio of the thickness of each layer (resin layer [II]/resin layer [I]/resin layer [II]) is 1/10/1, and the first It cooled between the cooling roll and the 2nd cooling roll (set temperature 50 degreeC), and obtained the sheet-like laminated body of thickness 1.6mm at the speed|rate of 0.7 m/min.

The said sheet-like laminated body was heated to the temperature of 140 degreeC, and it shape|molded by the vacuum pressure molding method using the cup-shaped metal mold|die, and obtained the container. On the other hand, the mold had an upper opening diameter: 70 mm, a bottom diameter: 60 mm, a depth: 70 mm, and a drawing ratio H/D: 1.0. In addition, the thickness of the resin layer [II] of the said container was 25 micrometers. About the said container, the said evaluation was performed. A result is shown in Table 2.

[Examples 2 to 12, Comparative Examples 1 to 11]

A sheet-like laminate was produced in the same manner as in Example 1 except that the raw materials and compositions of the resin compositions [I] and [II] were changed as shown in Tables 2 to 6. Moreover, similarly to Example 1, the said laminated body was shape|molded, the container was produced, and it evaluated. The results are shown in Tables 2 to 6. On the other hand, Millard R8000 (trade name, Dainichi Seika Kogyo Co., Ltd. make) was used as a nucleating agent in all. Moreover, in Example 12 and Comparative Examples 10 and 11, the single-layer sheet which consists of resin layer [I] was produced. Further, in Comparative Example 7, sagging occurred during heating, and molding into a container was not possible. Further, in Comparative Example 8, the laminate did not extend uniformly, and thus it was not possible to shape it into a container.

This application claims priority on the basis of Japanese application Japanese Patent Application No. 2015-6488 for which it applied on January 16, 2015, and takes in all the indications here.

As mentioned above, although this invention was demonstrated with reference to embodiment and an Example, this invention is not limited to the said embodiment and Example. Various changes that can be understood by those skilled in the art can be made within the scope of the present invention to the configuration and details of the present invention.

Claims (11)

Propylene-based polymer (A): 60.0 mass% or more and 83.0 mass% or less, and ethylene-based polymer (B): 17.0 mass% or more and 40.0 mass% or less (provided that (A) + (B) = 100.0 mass%). A resin layer [I] containing [I], and
Propylene-based polymer (A): 80.0 mass% or more and 99.9 mass% or less, and ethylene-based polymer (B): 0.0 mass% or more and less than 15.0 mass% and nucleating agent (C): 0.1 mass% or more and 20.0 mass% or less (provided that ( A) + (B) + (C) = 100.0 mass%) resin layer [II] containing the resin composition [II]
As a laminate comprising a,
In both of the resin compositions [I] and [II], the propylene-based polymer (A) and the ethylene-based polymer (B) satisfy the following requirements (i) to (iv).
Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.
Requirement (ii): The content of ?-olefins other than propylene determined by infrared spectroscopy in the propylene-based polymer (A) is 0 to 5% by mass.
Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .
Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0. The method of claim 1,
In both the resin compositions [I] and [II], the ethylene-based polymer (B) has a density of 891 to 945 kg/m ³ ethylene-based polymer (B1): 50.0 to 100.0 mass% and a density of 890 kg/m ³ The laminate which is a composition which consists of the following ethylene polymers (B2): 0.0-50.0 mass % (however, (B1)+(B2)=100.0 mass %). The method of claim 1,
The laminate consists of the resin layer [I] and the resin layer [II],
A laminate in which the ratio of the thickness of the resin layer [I] to the resin layer [II] (resin layer [II]/resin layer [I]) is 1/198 to 1/3. The method of claim 1,
The resin layer [II], the resin layer [I], and the resin layer [II] are laminated in this order,
A laminate in which the ratio of the thickness of each layer (resin layer [II]/resin layer [I]/resin layer [II]) is 1/198/1 to 1/3/1. The method of claim 1,
The laminate having a thickness of 3 mm or less. The method of claim 1,
A laminate in which the ?-olefin content other than propylene in the above requirement (ii) is ethylene content. The container which consists of the laminated body in any one of Claims 1-6. 8. The method of claim 7,
A container in which the resin layer [II] has a thickness of 1.5 µm or more. 8. The method of claim 7,
A container obtained by vacuum pressure molding the laminate. The manufacturing method of the container which carries out vacuum forming, air pressure forming, or vacuum air pressure forming of the laminated body in any one of Claims 1-6, and obtaining a container. Propylene-based polymer (A): 60.0% by mass or more and 83.0% by mass or less and ethylene-based polymer (B): 17.0% by mass or more and 40.0% by mass or less (provided that (A) + (B) = 100.0% by mass), A sheet for a laminate raw material satisfying the following requirements (i) to (v).
Requirement (i): According to JIS K6921, the propylene polymer (A) has a melt flow rate (MFR) of 0.1 to 12.0 g/10 min, measured at a temperature of 230°C and a load of 21.18 N.
Requirement (ii): The content of α-olefins other than propylene in the propylene-based polymer (A) determined by infrared spectroscopy is 0 to 5% by mass.
Requirement (iii): The density of the ethylene polymer (B) measured in accordance with JIS K6922 is 890 to 920 kg/m ³ .
Requirement (iv): MFR (A) measured at a temperature of 230°C and a load of 21.18N in accordance with JIS K6921 of the propylene-based polymer (A), and a temperature of 230°C in accordance with JIS K6921 of the ethylene-based polymer (B); The ratio (MFR(A)/MFR(B)) of MFR(B) measured under a load of 21.18N is 0.2 to 5.0.
Requirement (v): The thickness of the said sheet|seat for laminated body raw materials is 2.97 mm or less.